EP3604257B1

EP3604257B1 - Article comprising a fiber-reinforced self-healing bond coat

Info

Publication number: EP3604257B1
Application number: EP19189903.8A
Authority: EP
Inventors: Richard Wesley Jackson; John E. Holowczak; Xia Tang; James T. Beals
Original assignee: Raytheon Technologies Corp
Current assignee: RTX Corp
Priority date: 2018-08-03
Filing date: 2019-08-02
Publication date: 2022-04-06
Anticipated expiration: 2039-08-02
Also published as: EP3604257A1; US11668198B2; US20200040746A1

Description

BACKGROUND

The disclosure relates to an article comprising a substrate containing silicon and an environmental barrier coating (EBC) which functions as a protective environmental barrier coating and inhibits the formation of gaseous species of Si, particularly Si(OH)_x when the article is exposed to a high temperature, steam-laden environment.
Ceramic materials containing silicon and metal alloys containing silicon have been proposed for structures used in high temperature applications as, for example, gas turbine engines, heat exchangers, internal combustion engines, and the like. A particularly useful application for these materials is for service in gas turbine engines which operate at high temperatures in steam-laden environments. The ceramic materials that operate within the gas turbine are exposed to an environment in which jet fuel is combusted. As a result of the combustion, the temperature is high and steam (vapor phase water) and oxygen are present.
It has been found that these silicon containing substrates can recede and lose mass as a result of a formation of volatile Si species, particularly Si(OH)_x and SiO when exposed to high temperature, steam laden environments. For example, silicon carbide when exposed to a lean fuel environment of approximately 1 ATM pressure of water vapor at 1200°C will exhibit weight loss and recession at a rate of approximately 6 mils per 1000 hrs.
It is believed that the process involves oxidation of the silicon carbide to form silica on the surface of the silicon carbide followed by reaction of the silica with steam to form volatile species of silicon such as Si(OH)_x. Naturally it would be highly desirable to provide an external barrier coating for silicon containing substrates which would inhibit the formation of volatile silicon species, Si(OH)_x and SiO, and thereby reduce recession and mass loss. WO2014204480A1 , EP2615250A1 , EP189504A1 and EP2644747A2 disclose environmental barrier coatings of the prior art.

SUMMARY

In an aspect of the invention an article is provided in accordance with claim 1.
In another and alternative embodiment, the substrate comprises a ceramic matrix composite (CMC) material.
In another and alternative embodiment, the fiber-reinforcement structure comprises a SiC material composition.
In another and alternative embodiment, the substrate comprises a turbine blade, and the load bearing stress direction is oriented along a root to tip direction.
In another and alternative embodiment, the substrate comprises at least one of a turbine vane and a turbine blade, and the load bearing stress direction is oriented along the contour of a platform fillet.
In another and alternative embodiment, the fiber-reinforcement structure comprises fibers that are oxygen getter loading materials.
In another and alternative embodiment, the fiber-reinforcement structure comprises fibers that are coated with an interface coating.
In another and alternative embodiment, the interface coating is selected from the group consisting of boron nitride, silicon carbide, an oxide and carbon.
In another and alternative embodiment, the matrix comprises a multi-phase mixture.
In another and alternative embodiment, the multi-phase mixture comprises SiO₂.
In another and alternative embodiment, the self-healing phase comprises a glass phase.
In another and alternative embodiment, the self-healing phase comprises a material having properties of being in thermodynamic equilibrium with SiO₂ during operation at predetermined temperatures.
In another and alternative embodiment, the self-healing phase comprises a material having properties of flowing into cracks formed in the matrix during operation at predetermined temperatures of between 1000°C and 2000°C.
In another and alternative embodiment, the environmental barrier coating further comprises an oxygen getter phase interspersed throughout the matrix.
In another and alternative embodiment, the environmental barrier coating further comprises a protective layer applied on the environmental barrier coating.
The disclosure relates to a continuous fiber-reinforced, self-healing environmental barrier coating that prevents the ingress of oxygen and steam. The disclosed coating can increase durability with respect to conventional coatings. This coating consists of an oxide matrix and continuous fibers in a woven structure. The oxide matrix is a multi-phase mixture consisting of at least a SiO₂ rich phase and a glass phase. In alternative embodiments, the oxide matrix can be a single phase material that may not include a self-healing functionality. The composition of the glass phase is chosen to be in thermodynamic equilibrium with SiO₂ and to be sufficiently fluid at high temperatures to flow into cracks in the coating, which imparts 'self-healing functionality.' The fibers could be SiC, in some instances coated with an interface coating, such as boron nitride or silicon carbide, oxide (e.g. Nextel^™ 720) or carbon.
Other details of the coating are set forth in the following detailed description and the accompanying drawings wherein like reference numerals depict like elements.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross section of an exemplary coating on a substrate containing silicon according to the disclosure.
FIG. 2 is a cross section of an exemplary coating on a substrate containing silicon according to the disclosure.
FIG. 3 is cross section of the exemplary coating on a substrate containing silicon according to the disclosure.

DETAILED DESCRIPTION

Referring now to FIG. 1, there is illustrated an environmental barrier coating 10 formed over a substrate 12 of an article 14, configured to inhibit the formation of gaseous species of silicon when the article 14 is exposed to a high temperature, steam-laden environment. The coating 10 can be designed for maximum protection between 1100°C and 1700°C. The substrate 12 can be associated with articles 14 such as, at least one of a turbine vane and a turbine blade, and particularly a gas turbine engine component, such as components in the hot section of the gas turbine engine, including rotating components and portions of combustors, shrouds, and the like.
The substrate 12 of the article 14 can include portions that experience certain forces that result in a load bearing stress often oriented in a particular direction, i.e., a load bearing stress direction 16 of the substrate 12 of the article 14, illustrated as an arrow 16. It is contemplated that the load bearing stress direction 16 can be oriented in a variety of directions as well as multiple directions depending on the design of the substrate 12 and service of the article 14 in the gas turbine engine.
In an exemplary embodiment the load bearing stress direction 16 can be oriented from a root 18 of the article 14 to a tip 20 of the article 14, such as a blade root to a blade tip. In another exemplary embodiment, the load bearing stress direction 16 can be oriented along a contour of a fillet between a platform and an airfoil portion of the article 14, such as a blade/vane platform fillet 22. As illustrated in FIG 3, the root to tip direction can be understood as orthogonal to the plane of the page shown in the bundle of fibers 38.
The substrate 12 can be constructed from materials containing silicon and can be a ceramic matrix composite material, a silicon ceramic substrate or a silicon containing metal alloy. In an exemplary embodiment, the substrate 12 can be silicon containing ceramic material such as, for example, silicon carbide, silicon nitride, silicon oxy-nitride and silicon aluminum oxy-nitride. In accordance with a particular embodiment, the silicon containing ceramic substrate comprises a silicon containing matrix with reinforcing materials 24 such as fibers, particles and the like and, more particularly, a silicon based matrix which is fiber-reinforced. Particularly suitable ceramic substrates are a silicon carbide coated silicon carbide fiber-reinforced silicon carbide particle and silicon matrix, a carbon fiber-reinforced silicon carbide matrix and a silicon carbide fiber-reinforced silicon nitride matrix. Particularly useful silicon-metal alloys for use as substrates for the article 14 can include molybdenum-silicon alloys, niobium-silicon alloys, iron-silicon alloys, and aluminum-silicon alloys.
Referring also to FIG. 2 and FIG. 3, an environmental barrier layer 26 can be applied to the substrate 14. A protective layer 28 can be applied on the environmental barrier layer 26. The protective layer 28 is configured to resist vaporization when exposed to steam. In an exemplary embodiment, the protective layer can be a rare earth disilicate, such as Y₂Si₂O₇, Yb₂Si₂O₇; a rare earth monosilicate, such as Y₂SiO₅, Yb₂SiO₅, HfSiO₄, ZrSiO₄, HfO₂, BSAS (Ba_xSr_1-xAl₂Si₂O₈ where x may be 0.25) .
The environmental barrier layer 26 includes an oxide matrix 30 surrounding a fiber-reinforcement structure 32 and a self-healing phase 34 interspersed throughout the oxide matrix 30. In an alternative embodiment, not according to the invention, the oxide matrix 30 can be a single phase without self-healing phase present. In another embodiment, the oxide matrix 30 can include a multi-phase mixture, such as SiO₂ rich phase. The self-healing phase 34 can include a glass phase. The self-healing phase 34 can include a material having properties that are in thermodynamic equilibrium with SiO₂ during operation at predetermined temperatures. The self-healing phase 34 comprises a material having properties of flowing into cracks 48 formed in the matrix 30 during operation at those predetermined temperatures. The self-healing phase 34 can be sufficiently fluid at high temperatures to flow into cracks 48 in the coating 10, which imparts a self-healing functionality. Between 1000°C and 2000°C these materials can exist as mixtures of solid and liquid phases. The temperature at which liquid formation occurs can be controlled by the chemical composition. In an exemplary embodiment, liquid formation initiates between 1150°C and 1500°C, with the volume fraction of liquid increasing with temperature. The viscosity of the liquid phase can vary from 0.1 to 100,000 Pa*s with the exemplary viscosity varying between 10-10,000 Pa*s. An example of the self-healing phase 34 can include a mixture of BaMg₂Al₆Si₉O₃₀ and SiO₂. Another example can include the mixture of CaAl₂Si₂O₈, CaSiO₃ and SiO₂. Another example includes the mixture of Y₂Si₂O₇, Al₂O₃ and SiO₂. Alternatively, the materials listed above could be premixed and processed to form a glass. The initial composition of the glass could be: 2%BaO,3%MgO, 10%AlO_1.5, 85% SiO₂, or 8% CaO, 17%AlO_1.5 75% SiO₂, or 10% YO_1.5, 10 AlO_1.5, 80%SiO₂.
An oxygen getter phase 36 can also be interspersed throughout the oxide matrix 30. The oxygen getter phase 36 can comprise an oxy-carbide material. In an exemplary embodiment, the oxy-carbide material can include a glass that contains oxygen and carbon and silicon dioxide as well as particles of amorphous carbon and silicon carbide.
The fiber-reinforcement structure 32 includes a continuous weave of fibers. In an exemplary embodiment, the fiber-reinforcement structure 32 comprises a SiC material composition. The fiber-reinforcement structure 32 includes at least one first fiber bundle 38 oriented along the load bearing stress direction 16 of the substrate 12. In an exemplary embodiment, the first fiber bundle 38 can be oriented from blade root 18 to blade tip 20 and aligned along the root to tip direction, so as to provide structural support along the same orientation as the load bearing stress direction 16. In another exemplary embodiment, the first fiber bundle 38 can be oriented along the load bearing stress direction 16 oriented along the contour of the blade/vane platform fillet 22.
In accordance with the invention, the fiber-reinforcement structure 32 comprises at least one second fiber bundle 40 oriented orthogonal to the first fiber bundle 38 orientation. The fiber-reinforcement structure 32 also comprises at least one third fiber 42 woven between the first fiber bundle 38 and the second fiber bundle 40. In an exemplary embodiment, the fiber-reinforcement structure 32 comprises fibers that comprise oxygen getter materials 44. In another exemplary embodiment, the fiber-reinforcement structure 32 comprises fibers that are coated with an interface coating 46. The interface coating 46 can include materials selected from the group consisting of boron nitride, silicon carbide, an oxide and carbon.
The environmental barrier layer 26 can be present on the article at a thickness of greater than or equal to about 0.5 mils (0.0005 inch), preferably between about 3 to about 30 mils and ideally between about 3 to about 8 mils.
The environmental barrier layer 26 can be applied by preparing the substrate 14 surface.
There are several methods that could be used to introduce a glass-ceramic into the fiber reinforcement structure 32 being provided for the environmental barrier coating 10. In one approach, a fiber preform can be infiltrated using a glass particulate suspension, which would be added to the fiber preform layer by soaking, spraying or other means, at ambient temperature. The infiltrated fabric or preform is placed adjacent to the silicon containing CMC substrate 12, and the assembly is heated. Pressure can be applied using graphite dies, powdered media such as carbon or boron nitride, and the like, in order to de-gas the environmental barrier layer 26 at temperatures suitable for melting the glass. The subsequent assembly can undergo annealing to obtain a desired microstructure.
In another exemplary embodiment, an alternate technique of assembly would be to place a fiber preform in contact with the silicon containing CMC substrate 12. The fiber perform can then be rigidized using a variety of techniques, including but not limited to adding a ceramic sol and freezing the substrate followed by freeze drying. The assembly is then placed into a graphite die which comprises an outer profile of the EBC coated article 14. Molten glass is then injected into the die and flows into and among the fibers of the preform. The assembly can then be cooled and (re)heated to a temperature suitable to promote the formation of the desired microstructure.
Alternative approaches to introducing oxide or silicate phases into a relatively thin fiber preform, can include but are not limited to spraying the preform with a suspension, followed by heating the surface via flame or plasma spraying molten oxide and/or silicate materials onto the preform, and the like. Generally, avoiding sharp temperature gradients between the substrate and the created layer should be avoided to enhance adherence.
A self-healing, fiber-reinforced oxidant barrier offers a robust mechanism for protecting load bearing materials in the hot-section of gas turbine engines. This disclosure describes the use of fiber reinforcements in the environmental barrier coating to increase durability. Additionally, the self-healing, multi-phase matrix that surrounds the fibers inhibits the permeability of oxidants through the coating. The fibers will also increase the creep resistance of the coating, enhancing durability on rotating components.
An environmental barrier coating prevents CMC recession caused by Si(OH)x formation. Interaction of the environmental barrier coating with the steam laden combustion environment results in the formation of Si(OH)x, but the rate of formation is much less than that of an uncoated SiC CMC.
There has been provided a coating. While the coating has been described in the context of specific embodiments thereof, other unforeseen alternatives, modifications, and variations may become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations which fall within the broad scope of the appended claims.

Claims

An article comprising:
a substrate (12) containing silicon; and

an environmental barrier coating (10), the environmental barrier coating (10) comprising:
an environmental barrier layer (26) applied to the substrate (12); said environmental barrier layer (26) comprising an oxide matrix (30) surrounding a fiber-reinforcement structure (32) and a self-healing phase (34) interspersed throughout said oxide matrix (30), wherein said self-healing phase (34) comprises a material configured to form a liquid and be sufficiently fluid to flow into cracks (48) formed in said oxide matrix (30) during operation at predetermined temperatures;

wherein said fiber-reinforcement structure (32) comprises a continuous weave of fibers;

wherein the substrate (12) includes portions that are configured to experience forces in a load bearing stress direction (16);

wherein said fiber-reinforcement structure (32) comprises at least one first fiber bundle (38) oriented along the load bearing stress direction (16) of said substrate (12);

wherein said fiber-reinforcement structure (32) comprises at least one second fiber bundle (40) oriented orthogonal to said first fiber bundle (38) orientation;
wherein said fiber reinforcement structure (32) comprises at least one third fiber (42) woven between said first fiber bundle (38) and said second fiber bundle (40).
The article of claim 1, wherein said substrate (12) comprises a ceramic matrix composite material.
The article of claim 1 or 2, wherein said fiber-reinforcement structure (32) comprises a SiC material composition.
The article of any preceding claim, wherein the article (14) comprises a turbine blade, and said load bearing stress direction (16) is oriented along a root (18) to tip (20) direction of the turbine blade.
The article of any of claims 1-3, wherein said article (14) comprises at least one of a turbine vane and a turbine blade, and said load bearing stress direction (16) is oriented along a contour of a fillet (22) between a platform and an airfoil portion of the article (14).
The article of any preceding claim, wherein the environmental barrier coating further comprises an oxygen getter phase (36) interspersed throughout said matrix, wherein the oxygen getter phase (36) comprises an oxy-carbide material.
The article of any preceding claim, wherein said fiber-reinforcement structure (32) comprises fibers that are coated with an interface coating (46).
The article of claim 7, wherein said interface coating (46) is selected from the group consisting of boron nitride, silicon carbide, an oxide and carbon.
The article of any preceding claim, wherein said oxide matrix (30) comprises a multi-phase mixture.
The article of claim 9, wherein said multi-phase mixture comprises SiO₂.
The article of any preceding claim, wherein said self-healing phase (34) comprises a glass phase.
The article of any preceding claim, the material is configured to be in thermodynamic equilibrium with SiO₂ during operation at the predetermined temperatures.
The article of any preceding claim, wherein the predetermined temperatures are between 1000°C and 2000°C.
The article of any preceding claim, wherein the material is configured to initiate forming the liquid at a temperature between 1150°C and 1500°C.
The article of any preceding claim, further comprising:
a protective layer (28) configured to resist vaporization when exposed to steam applied on said environmental barrier coating (10).